Laundry detergent compositions with amino acid based polymers to provide appearance and integrity benefits to fabrics laundered therewith

ABSTRACT

Modified polyaspartic acids are obtained by polycondensing (a) 1 to 99.9 mol % aspartic acid with (b) 99 to 0.1 mol % fatty acids, polybasic carboxylic acids, anhydrides of polybasic carboxylic acids, polybasic hydroxycarboxylic acids, monobasic poly-hydroxycarboxylic acids, alcohols, amines, alkoxylated alcohols and amines, amino sugars, carbohydrates, sugar carboxylic acids and/or non-proteinogenic aminocarboxylic acids, or by polymerizing monoethylenically unsaturated monomers in the presence of polyaspartic acids, in the manner of radically initiated graft copolymerization. Also disclosed is a process for preparing these modified polyaspartic acids, as well as the use of these modified polyaspartic acids as additives to washing and cleaning agents, as water conditioning agents and as deposit inhibitors during the condensation of sugar juice.

This application claims priority from provisional application No.60/055,152, filed Aug. 8, 1997.

TECHNICAL FIELD

The present invention relates to compositions, in either liquid orgranular form, for use in laundry applications, wherein the compositionscomprise certain amino acid based polymer, oligomer or copolymermaterials which impart appearance and integrity benefits to fabrics andtextiles laundered in washing solutions formed from such compositions.

BACKGROUND OF THE INVENTION

It is, of course, well known that alternating cycles of using andlaundering fabrics and textiles, such as articles of worn clothing andapparel, will inevitably adversely affect the appearance and integrityof the fabric and textile items so used and laundered. Fabrics andtextiles simply wear out over time and with use. Laundering of fabricsand textiles is necessary to remove soils and stains which accumulatetherein and thereon during ordinary use. However, the launderingoperation itself, over many cycles, can accentuate and contribute to thedeterioration of the integrity and the appearance of such fabrics andtextiles.

Deterioration of fabric integrity and appearance can manifest itself inseveral ways. Short fibers are dislodged from woven and knitfabric/textile structures by the mechanical action of laundering. Thesedislodged fibers may form lint, fuzz or “pills” which are visible on thesurface of fabrics and diminish the appearance of newness of the fabric.Further, repeated laundering of fabrics and textiles, especially withbleach-containing laundry products, can remove dye from fabrics andtextiles and impart a faded, worn out appearance as a result ofdiminished color intensity, and in many cases, as a result of changes inhues or shades of color.

Given the foregoing, there is clearly an ongoing need to identifymaterials which could be added to laundry detergent products that wouldassociate themselves with the fibers of the fabrics and textileslaundered using such detergent products and thereby reduce or minimizethe tendency of the laundered fabric/textiles to deteriorate inappearance. Any such detergent product additive material should, ofcourse, be able to benefit fabric appearance and integrity withoutunduly interfering with the ability of the laundry detergent to performits fabric cleaning function. The present invention is directed to theuse of amino acid based polymer, oligomer or copolymer materials inlaundry applications which perform in this desired manner.

SUMMARY OF THE INVENTION

Amino acid based polymer, oligomer or copolymer materials which aresuitable for use in laundry operations and provide the desired fabricappearance and integrity benefits can be characterized by the followinggeneral formula:

wherein the polymer, oligomer, or copolymer contains at least about 5mole %, preferably at least about 10 mole %, more preferably from about20 mole %, and most preferably at least about 40 mole %, of a basicamino acid;

each R₁ is selected from the group consisting of H, C₁-C₁₈ saturated orunsaturated, branched or linear alkyl, C₂-C₁₈ saturated or unsaturated,branched or linear hydroxyalkyl, C₃-C₈ cycloalkyl, C₆-C₁₈ aryl, andC₇-C₁₈ alkylaryl;

each R₂ is independently selected from the group consisting of H, NH₂,

each R₃ is independently selected from the group consisting of OH, OM,N(R₁)₂,

each R₅ is independently selected from the group consisting of C₁-C₁₂linear or branched alkylene, cyclic alkylene, C₂-C₁₂ linearoxa-substituted alkylene, C₂-C₁₂ branched oxa-substituted alkylene,C₃-C₁₂ cyclic oxa-substituted alkylene, and

 wherein:

each x is independently from 0 to about 200;

each y is independently from 0 to about 10, preferably y is 0, 3, or 4,and most

preferably y is 4;

each z is independently from 1 to about 7;

each a is independently from about 1 to about 12;

M is selected from compatible cations; and

provided that:

the sum of all x's is from 2 to about 200, preferably from about 3 toabout 150, more preferably from about 5 to about 120, and mostpreferably from about 5 to about 100;

any basic amine site on the polymer, oligomer, or copolymer may beoptionally protonated, alkylated, or quaternized with groups selectedfrom the group consisting of H, CH₃, alkyl, hydroxyalkyl, benzyl andmixtures thereof;

any amine site may be optionally alkoxylated; and

when two R₁ groups are attached to a common nitrogen the two R₁s mayform a cyclic structure selected from the group consisting of C₅-C₈alkylene, and C₄-C₇ alkyleneoxyalkylene.

The amino acid based polymer, oligomer or copolymer materials definedabove can be used as a washing solution additive in either granular orliquid form. Alternatively, they can be admixed to granular detergents,dissolved in liquid detergent compositions or added to a fabricsoftening composition. Preferably the fabric treatment compositions ofthis invention comprise from about 0.1% to about 10%, preferably fromabout 0.2% to about 8%, more preferably from about 0.3% to about 6%, andmost preferably from about 0.4% to about 5%, by weight of a mixture ofthe amino acid based polymers, oligomers or copolymers defiened by thegeneral formula above. The forgoing description of uses for the aminoacid based fabric treatment materials defined herein are intended to beexemplary and other uses will be apparent to those skilled in the artand are intended to be within the scope of the present invention.

The laundry detergent compositions herein comprise from about 1% to 80%by weight of a detersive surfactant, from about 0.1% to 80% by weight ofan organic or inorganic detergency builder and from about 0.1% to 5% byweight of the amino acid based fabric treatment materials of the presentinvention. The detersive surfactant and detergency builder materials canbe any of those useful in conventional laundry detergent products.

Aqueous solutions of the amino acid based polymer, oligomer or copolymermaterials of the subject invention comprise from about 0.1% to 50% byweight of the amino acid based fabric treatment materials dissolved inwater and other ingredients such as stabilizers and pH adjusters.

In its method aspect, the present invention relates to the laundering ortreating of fabrics and textiles in aqueous washing or treatingsolutions formed from effective amounts of the detergent compositionsdescribed herein, or formed from the individual components of suchcompositions. Laundering of fabrics and textiles in such washingsolutions, followed by rinsing and drying, imparts fabric appearancebenefits to the fabric and textile articles so treated. Such benefitscan include improved overall appearance, pill/fuzz reduction,antifading, improved abrasion resistance, and/or enhanced softness.

DETAILED DESCRIPTION OF THE INVENTION

As noted, when fabric or textiles are laundered in wash solutions whichcomprise the amino acid based polymer, oligomer or copolymer materialsof the present invention fabric appearance and integrity are enhanced.The amino acid based fabric treatment materials can be added to washsolutions by incorporating them into a detergent composition, a fabricsoftener or by adding them separately to the washing solution. The aminoacid based fabric treatment materials are described herein primarily asliquid or granular detergent additives but the present invention is notmeant to be so limited. The amino acid based fabric treatment materials,detergent composition components, optional ingredients for suchcompositions and methods of using such compositions, are described indetail below. All percentages are by weight unless other specified.

A) Amino Acid Based Polymer Oligomer or Copolymer Materials

The essential component of the compositions of the present inventioncomprises one or more amino acid based polymer, oligomer or copolymer.Such materials have been found to impart a number of appearance benefitsto fabrics and textiles laundered in aqueous washing solutions formedfrom detergent compositions which contain such amino acid based fabrictreatment materials. Such fabric appearance benefits can include, forexample, improved overall appearance of the laundered fabrics, reductionof the formation of pills and fuzz, protection against color fading,improved abrasion resistance, etc. The amino acid based fabric treatmentmaterials used in the compositions and methods herein can provide suchfabric appearance benefits with acceptably little or no loss in cleaningperformance provided by the laundry detergent compositions into whichsuch materials are incorporated.

The amino acid based polymer, oligomer or copolymer component of thecompositions herein may comprise combinations of these amino acid basedmaterials. For example, a mixture of lysine and hexamethylenediaminecondensates can be combined with a mixture of lysine and octylaminecondensates to achieve the desired fabric treatment results. Moreover,the molecular weight of amino acid based fabric treatment materials canvary within the mixture as is illustrated in Example I below.

As will be apparent to those skilled in the art, an oligomer is amolecule consisting of only a few monomer units while polymers compriseconsiderably more monomer units. For the present invention, oligomersare defined as molecules having an average molecular weight below about1,000 and polymers are molecules having an average molecular weight ofgreater than about 1,000. Copolymers are polymers or oligomers whereintwo or more dissimilar monomers have been simultaneously or sequentiallypolymerized. Copolymers of the present invention can include, forexample, polymers or oligomers polymerized from a mixture of a primaryamino acid based monomer, e.g., lysine, and a secondary amino acidmonomer, e.g., tryptophan.

The amino acid based fabric treatment component of the detergentcompositions herein will generally comprise from about 0.1% to about10%, preferably from about 0.2% to about 8%, more preferably from about0.3% to about 6%, and most preferably from about 0.4% to about 5%, byweight of a mixture of the amino acid based polymers, oligomers orcopolymers defiened by the general formula below. But when used as awashing solution additive, i.e. when the amino acid based fabrictreatment component is not incorporated into a detergent composition,the concentration of the amino acid based component can comprise fromabout 0.1% to about 50% by weight of the additive material.

One suitable group of amino acid based polymer, oligomer or copolymermaterials for use herein is characterized by the following formula:

wherein the polymer, oligomer, or copolymer contains at least about 5mole %, preferably at least about 10 mole %, more preferably from about20 mole %, and most preferably at least about 40 mole %, of a basicamino acid;

each R₁ is selected from the group consisting of H, C₁-C₁₈ saturated orunsaturated, branched or linear alkyl, C₂-C₁₈ saturated or unsaturated,branched or linear hydroxyalkyl, C₃-C₈ cycloalkyl, C₆-C₁₈ aryl, andC₇-C₁₈ alkylaryl;

each R₂ is independently selected from the group consisting of H, NH₂,

each R₃ is independently selected from the group consisting of OH, OM,N(R₁)₂,

each R₅ is independently selected from the group consisting of C₁-C₁₂linear or branched alkylene, cyclic alkylene, C₂-C₁₂ linearoxa-substituted alkylene, C₂-C₁₂ branched oxa-substituted alkylene,C₃-C₁₂ cyclic oxa-substituted alkylene, and

 wherein:

each x is independently from 0 to about 200;

each y is independently from 0 to about 10;

each z is independently from 1 to about 7;

each a is independently from about 1 to about 12;

M is selected from compatible cations; and

provided that:

the sum of all x's is from 2 to about 200, preferably from about 3 toabout 150, more preferably from about 5 to about 120, and mostpreferably from about 5 to about 100;

any basic amine site on the polymer, oligomer, or copolymer may beoptionally protonated, alkylated, or quaternized with groups selectedfrom the group consisting of H, CH₃, alkyl, hydroxyalkyl, benzyl andmixtures thereof;

any amine site may be optionally alkoxylated; and

when two R₁ groups are attached to a common nitrogen the two R₁s mayform a cyclic structure selected from the group consisting of C₅-C₈alkylene, and C₄-C₇ alkyleneoxyalkylene.

Preferred amino acid based polymer, oligomer or copolymer materials foruse herein include lysine and hexamethylenediamine condensates of thegeneral formula:

wherein x and y are individually from 0 to about 50, provided thatx+y>0. As is illustrated in Example I below, the lysine andhexamethylenediamine condensates of the present invention are often amixture of various molecules having different values for x+y. Especiallypreferred lysine and hexamethylenediamine condensates have x+y equal tofrom about 2 to about 5. The above, simplified structure depiction ismeant to include also those oligomers and polymers with more branchingwhich arise from amide bond linkages formed at the alpha aimino groupand from amide bond linkages formed at both amino groups of a singlelysine-derived unit.

Compositions which are also preferred for use herein are lysine andoctylamine condensates of the general formula:

wherein x is from about 1 to about 50.

Additionally preferred compositions for use herein are lysine andtryptophan condensates of the general formula:

Wherein p and q independently are from about 1 to about 50.

Synthesis of the amino acid based polymer, oligomer or copolymermaterials defined herein will be apparent to those skilled in the art inlight of Example I wherein the synthesis of 5:1, L-Lysine:1,6-Hexanediamine is exemplified. Example I details the condensationreaction of lysine and hexanediamine which produces a preferred productfor achieving the desired fabric appearance and integrity benefits ofthe present invention. However, other amines are equally suitable forcondensation reactions with amino acids such as lysine, and thosesuitable amines which are readily available and/or possess interestingstructural characteristics include:

aliphatic and cycloaliphatic amines, preferably methylamine, ethylamine,proplyamine, butylamine, pentylamine, hexylamine, heptylamine,ethylhexylamine, octylamine, nonylamine, decylamine, undecylamine,dodecylamine, tridecylamine, stearylamine, palmitylamine,2-ethylhexylamine, isononylamine, hexamethyleneimine, dimethylamine,diethylamine, dipropylamine, dibutylamine, dihexylamine,ditridecylamine, N-methylbutylamine, N-ethylbutylamine;

alkoxyalkylamines, preferably 2-methoxyethylamine, 2-ethoxyethylamine,3-methoxypropylamine, 3-ethoxypropylamine,3-[(2-ethylhexyl)oxy]-1-propanamine, 3-(2-methoxyethoxy)-1-propanamine,2-methoxy-N-(2-methoxyethyl)ethanamine;

alicyclic amines, preferably cyclopentylamine, cyclohexylamine,N-methycyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine;

diamines, triamines and tetramines, preferably ethylenediamine,propylenediamine, butylenediamine, neopentyldiamine,hexamethylenediamine, octamethylenediamine, imidazole,5-amino-1,3,-trimethylcyclohexylmethylamine,4,4′-methylenebiscyclohexylamine,4,4′-methylenebis(2-methylcyclohexylamine), 4,7-dioxadecyl-1,10-diamine,4,9-dioxadodecyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine,2-(ethylamino)ethylamine, 3-(methylamino)propylamine,3-(cyclohexylamino)propylamine, 3-(2-aminoethyl) aminopropylamine,2-(diethylamino)ethylamine, 3-(dimethylamino)propylamine;

dimethyldipropylenetriamine, 4-aminomethyloctane-1,8-diamine,3-(diethylamino)propylamine, N,N-diethyl-1,4-pentanediamine,diethylenetriamine, dipropylenetriamine, bis(hexamethylene)triamine,aminoethylpiperazine, aminopropylpiperazine,N,N-bis(aminopropyl)methylamine, N,N-bis(aminopropyl)ethylamine,N,N-bis(aminoproply)methylamine, N,N-bis(aminopropyl)ethylamine,N,N-bis(aminopropyl)hexylamine, N,N-bis(aminopropyl)octylamine,N,N-dimethyldipropylenetriamine, N,N-bis(3-dimethylaminopropyl)amine,N,N″-1,2-ethanediylbis-(1,3-propanediamine), N-(aminoethyl)piperazine,N-(2-imidazole)piperazine, N-ethylpiperazine,N-(hydroxyethyl)piperazine, N-(aminoethyl)piperazine,N-(aminopropyl)piperazine, N-(aminoethyl)morpholine,N-(aminopropyl)morpholine, N-(aminoethyl)imidazole,N-(aminopropyl)imidazole, N-(aminoethyl)hexamethylenediamine,N-(aminopropyl)hexamethylenediamine, N-(aminoethyl)ethylenediamine,N-(aminopropyl)ethylenediamine, N-(aminoethyl)butylenediamine,N-(aminopropyl)butylenediamine, bis(aminoethyl)piperazine,bis(aminopropyl)piperazine, bis(aminoethyl)hexamethylenediamine,bis(aminopropyl)hexamethylenediamine, bis(aminoethyl)ethylenediamine,bis(aminopropyl)ethylenediamine, bis(aminoethyl)butylenediamine,bis(aminopropyl)butylenediamine;

aliphatic amino alcohols, preferably 2-aminoethanol, 3-amino-1propanol,1-amino-2-propanol, 2-(2-aminoethoxy)ethanol,2-[(2-aminoethyl)amino]ethanol, 2-methylaminoethanol,2-(ethylamino)ethanol, 2-butylaminoethanol, diethanolamine,3-[(2-hydroxyethyl)amino]-1-propanol, diisopropanolamine,bis(hydroxyethyl)aminoethylamine, bis(hydroxypropyl)aminoethylamine,bis(hydroxyethyl)aminopropylamine, bis(hydroxypropyl)aminopropylamine;

monoamino carboxylic acids, preferably glycine, alanine, sarcosine,asparagine, glutamine, 6-aminocaproic acid, caprolactam, 4-aminobutyricacid; and

glucosamine, melamine, urea, guanidine, polyguanides, piperidine,morpholine, 2,6-dimethylmorpholine.

B) Detersive Surfactant

The detergent compositions herein comprise from about 1% to 80% byweight of a detersive surfactant. Preferably such compositions comprisefrom about 5% to 50% by weight of surfactant. Detersive surfactantsutilized can be of the anionic, nonionic, zwitterionic, amnpholytic orcationic type or can comprise compatible mixtures of these types.Detergent surfactants useful herein are described in U.S. Pat. No.3,664,961, Norris, issued May 23, 1972, U.S. Pat. No. 3,919,678,Laughlin et al., issued Dec. 30, 1975, U.S. Pat. No. 4,222,905,Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy,issued Dec. 16, 1980. All of these patents are incorporated herein byreference. Of all the surfactants, anionics and nonionics are preferred.

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoap.

Additional non-soap anionic surfactants which are suitable for useherein include the water-soluble salts, preferably the alkali metal, andammonium salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 10 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester group. (Includedin the term “alkyl” is the alkyl portion of acyl groups.) Examples ofthis group of synthetic surfactants are a) the sodium, potassium andammonium alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈-C₁₈ carbon atoms) such as those produced by reducingthe glycerides of tallow or coconut oil; b) the sodium, potassium andammonium alkyl polyethoxylate sulfates, particularly those in which thealkyl group contains from 10 to 22, preferably from 12 to 18 carbonatoms, and wherein the polyethoxylate chain contains from 1 to 15,preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassiumalkylbenzene sulfonates in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 13, abbreviated as C₁₁₋₁₃ LAS.

Preferred nonionic surfactants are those of the formula R₁(OC₂H₄)_(n)OH,wherein R₁ is a C₁₀-C₁₆ alkyl group or a C₈-C₁₂ alkyl phenyl group, andn is from 3 to about 80. Particularly preferred are condensationproducts of C₁₂-C₁₅ alcohols with from about 5 to about 20 moles ofethylene oxide per mole of alcohol, e.g., C₁₂-C₁₃ alcohol condensed withabout 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable nonionic surfactants include polyhydroxy fatty acidamides of the formula:

wherein R is a C₉₋₁₇ alkyl or alkenyl, R₁ is a methyl group and Z isglycityl derived from a reduced sugar or alkoxylated derivative thereof.Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methylN-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acidamides are known and can be found in Wilson, U.S. Pat. No. 2,965,576 andSchwartz, U.S. Pat. No. 2,703,798, the disclosures of which areincorporated herein by reference.

Preferred surfactants for use in the detergent compositions describedherein are amine based surfactants of the general formula:

wherein R₁ is a C₆-C₁₂ alkyl group; n is from about 2 to about 4, X is abridging group which is selected from NH, CONH, COO, or O or X can beabsent; and R₃ and R₄ are individually selected from H, C₁-C₄ alkyl, or(CH₂—CH₂—O(R₅)) wherein R₅ is H or methyl. Especially preferred aminesbased surfactants include the following:

R_(1—(CH) ₂)₂-NH₂

R_(1—O—(CH) ₂)₃-NH₂

 R₁—C(O)—NH—(CH₂)₃-N(CH₃)₂

wherein R₁ is a C₆-C₁₂ alkyl group and R₅ is H or CH₃. Particularlypreferred amines for use in the surfactants defined above include thoseselected from the group consisting of octyl amine, hexyl amine, decylamine, dodecyl amine, C₈-C₁₂ bis(hydroxyethyl)amine, C₈-C₁₂bis(hydroxyisopropyl)amine, C₈-C₁₂ amido-propyl dimethyl amine, ormixtures thereof.

In a highly preferred embodiment, the amine based surfactant isdescribed by the formula:

R₁—C(O)—NH—(CH₂)₃—N(CH₃)₂

wherein R₁ is C₈-C₁₂ alkyl.

C) Detergent Builder

The detergent compositions herein may also comprise from about 0.1% to80% by weight of a detergent builder. Preferably such compositions inliquid form will comprise from about 1% to 10% by weight of the buildercomponent. Preferably such compositions in granular form will comprisefrom about 1% to 50% by weight of the builder component. Detergentbuilders are well known in the art and can comprise, for example,phosphate salts as well as various organic and inorganic nonphosphorusbuilders.

Water-soluble, nonphosphorus organic builders useful herein include thevarious alkali metal, ammonium and substituted ammonium polyacetates,carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples ofpolyacetate and polycarboxylate builders are the sodium, potassium,lithium, ammonium and substituted ammonium salts of ethylene diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melliticacid, benzene polycarboxylic acids, and citric acid. Other suitablepolycarboxylates for use herein are the polyacetal carboxylatesdescribed in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 toCrutchfield et al., and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 toCrutchfield et al., both of which are incorporated herein by reference.Particularly preferred polycarboxylate builders are the oxydisuccinatesand the ether carboxylate builder compositions comprising a combinationof tartrate monosuccinate and tartrate disuccinate described in U.S.Pat. No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure ofwhich is incorporated herein by reference.

Examples of suitable nonphosphorus, inorganic builders include thesilicates, aluminosilicates, borates and carbonates. Particularlypreferred are sodium and potassium carbonate, bicarbonate,sesquicarbonate, tetraborate decahydrate, and silicates having a weightratio of SiO₂ to alkali metal oxide of from about 0.5 to about 4.0,preferably from about 1.0 to about 2.4. Also preferred arealuminosilicates including zeolites. Such materials and their use asdetergent builders are more fully discussed in Corkill et al., U.S. Pat.No. 4,605,509, the disclosure of which is incorporated herein byreference. Also discussed in U.S. Pat. No. 4,605,509 are crystallinelayered silicates which are suitable for use in the detergentcompositions of this invention.

D) Optional Detergent Ingredients

In addition to the surfactants, builders and amino acid based polymer,oligomer or copolymer materials hereinbefore described, the detergentcompositions of the present invention can also include any number ofadditional optional ingredients. These include conventional detergentcomposition components such as enzymes and enzyme stabilizing agents,suds boosters or suds suppressers, anti-tarnish and anticorrosionagents, soil suspending agents, soil release agents, germicides, pHadjusting agents, non-builder alkalinity sources, chelating agents,organic and inorganic fillers, solvents, hydrotropes, opticalbrighteners, dyes and perfumes.

pH adjusting agents may be necessary in certain applications where thepH of the wash solution is greater than about 10.0 because the fabricintegrity benefits of the defined compositions begin to diminish at ahigher pH. Hence, if the wash solution is greater than about 10.0 afterthe addition of the amino acid based polymer, oligomer or copolymermaterials of the present invention a pH adjuster should be used toreduce the pH of the washing solution to below about 10.0, preferably toa pH of below about 9.5 and most preferably below about 7.5. Suitable pHadjusters will be known to those skilled in the art.

Normally, a preferred optional ingredient for incorporation intodetergent compositions is a bleaching agent, e.g., a peroxygen bleach.However, many common bleaching agents will degrade some, but not all, ofthe amino acid based fabric treatment materials of the presentinvention. Hence, before adding a bleaching agent to a detergentcomposition comprising an amino acid based fabric treatment material asdefined herein compatibility between the bleaching agent and the aminoacid based fabric treatment material must be investigated.

Another highly preferred optional ingredient in the detergentcompositions herein is a detersive enzyme component. While it is knownthat some enzymes will degrade the peptide bonds of amino acids, theamino acid based polymer, oligomer or copolymer materials defined hereindo not exhibit such degradation in the presence of enzymes. Hence,enzymes can be added to detergent compositions which comprise the aminoacid based fabric treatment materials of the present invention withsubstantially no degradation.

Enzymes can be included in the present detergent compositions for avariety of purposes, including removal of protein-based,carbohydrate-based, or triglyceride-based stains from substrates, forthe prevention of refugee dye transfer in fabric laundering, and forfabric restoration. Suitable enzymes include proteases, amylases,lipases, cellulases, peroxidases, and mixtures thereof of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.Preferred selections are influenced by factors such as pH-activityand/or stability, optimal thermostability, and stability to activedetergents, builders and the like. In this respect bacterial or fungalenzymes are preferred, such as bacterial amylases and proteases, andfungal cellulases. “Detersive enzyme”, as used herein, means any enzymehaving a cleaning, stain removing or otherwise beneficial effect in alaundry detergent composition. Preferred enzymes for laundry purposesinclude, but are not limited to, proteases, cellulases, lipases,amylases and peroxidases.

Enzymes are normally incorporated into detergent compositions at levelssufficient to provide a “cleaning-effective amount”. The term“cleaning-effective amount” refers to any amount capable of producing acleaning, stain removal, soil removal, whitening, deodorizing, orfreshness improving effect on substrates such as fabrics. In practicalterms for current commercial preparations, typical amounts are up toabout 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzymeper gram of the detergent composition. Stated otherwise, thecompositions herein will typically comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition. Higher active levels may be desirablein highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble. When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 10. U.S. Pat. No.4,435,307, Barbesgoard et al., Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also, the lipase inJapanese Patent Application 53,20487, laid open Feb. 24, 1978. Thislipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,under the trade name Lipase P “Amano,” or “Amano-P.” Other suitablecommercial lipases include Amano-CES, lipases ex Chromobacter viscosum,e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo JozoCo., Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein.

The enzyme-containing compositions herein may optionally also comprisefrom about 0.001% to about 10%, preferably from about 0.005% to about8%, most preferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such a system maybe inherently provided by other formulation actives, or be addedseparately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, and mixtures thereof, and are designedto address different stabilization problems depending on the type andphysical form of the detergent composition.

E) Detergent Composition Preparation

The detergent compositions according to the present invention can be inliquid, paste or granular form. Such compositions can be prepared bycombining the essential and optional components in the requisiteconcentrations in any suitable order and by any conventional means.

Granular compositions, for example, are generally made by combining basegranule ingredients, e.g., surfactants, builders, water, etc., as aslurry, and spray drying the resulting slurry to a low level of residualmoisture (5-12%). The remaining dry ingredients, e.g., granules of theessential amino acid based fabric treatment materials, can be admixed ingranular powder form with the spray dried granules in a rotary mixingdrum. The liquid ingredients, e.g., solutions of the essential aminoacid based fabric treatment materials, enzymes, binders and perfumes,can be sprayed onto the resulting granules to form the finisheddetergent composition. Granular compositions according to the presentinvention can also be in “compact form”, i.e. they may have a relativelyhigher density than conventional granular detergents, i.e. from 550 to950 g/l. In such case, the granular detergent compositions according tothe present invention will contain a lower amount of “inorganic fillersalt”, compared to conventional granular detergents; typical fillersalts are alkaline earth metal salts of sulphates and chlorides,typically sodium sulphate; “compact” detergents typically comprise notmore than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be in“compact form”, in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents. Addition of the amino acidbased polymer, oligomer or copolymer materials to liquid detergent orother aqueous compositions of this invention may be accomplished bysimply mixing into the liquid solutions the desired amino acid basedfabric treatment materials.

F) Fabric Laundering Method

The present invention also provides a method for laundering fabrics in amanner which imparts fabric appearance benefits provided by the aminoacid based polymer, oligomer or copolymer materials used herein. Such amethod employs contacting these fabrics with an aqueous washing solutionformed from an effective amount of the detergent compositionshereinbefore described or formed from the individual components of suchcompositions. Contacting of fabrics with washing solution will generallyoccur under conditions of agitation although the compositions of thepresent invention may also be used to form aqueous unagitated soakingsolutions for fabric cleaning and treatment. As discussed above, it ispreferred that the washing solution have a pH of less than about 10.0,preferably it has a pH of about 9.5 and most preferably it has a pH ofabout 7.5.

Agitation is preferably provided in a washing machine for good cleaning.Washing is preferably followed by drying the wet fabric in aconventional clothes dryer. An effective amount of a high density liquidor granular detergent composition in the aqueous wash solution in thewashing machine is preferably from about 500 to about 7000 ppm, morepreferably from about 1000 to about 3000 ppm.

G) Fabric Conditioning

The amino acid based polymer, oligomer or copolymer materialshereinbefore described as components of the laundry detergentcompositions herein may also be used to treat and condition fabrics andtextiles in the absence of the surfactant and builder components of thedetergent composition embodiments of this invention. Thus, for example,a fabric conditioning composition comprising only the amino acid basedfabric treatment materials themselves, or comprising an aqueous solutionof the amino acid based fabric treatment materials, may be added duringthe rinse cycle of a conventional home laundering operation in order toimpart the desired fabric appearance and integrity benefits hereinbeforedescribed.

EXAMPLES

The following examples illustrate the compositions and methods of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention.

Example I

The synthesis of an amino acid based polymer, specifically, 5:1 molarratio of L-Lysine: 1,6-Hexanediamine, is exemplified below. As usedherein, unless otherwise stated, all ratios are molar ratios of theinitial reactants, i.e., monomers. More specifically, L-lysine (suppliedby Aldrich, 1078.7 g, 7.38 moles), 1,6-hexanediamine (supplied byAldrich, 171.5 g, 1.48 moles), and propylene glycol (supplied by Baker,approximately 1 L) are added to a 5L, three neck, round bottom flaskwhich is equipped with a magnetic stirring bar, modified Claisen head,condenser (set for distillation), thermometer, and temperaturecontroller (Therm-O-Watch, I²R). The solution is blanketed with argonand heated at 170° C. for 4 hrs as water distills from the reaction. A¹³C-NMR (D₂O) shows the emergence of a peak at approximately 177 ppmwhich corresponds to an amide product. A smaller peak at approximately181 ppm may represent some unreacted L-lysine. The bulk solution is thendivided into six 1L round bottom flasks, and each flask is heated on aKugelrohr apparatus (Aldrich) at approximately 170° C. and approximately2 mm Hg for 3 hrs to remove solvent and volatile products. The flasksare cooled to room temperature to afford 915 g of dark brown, thickliquid. A ¹³C-NMR (D₂O) shows that the peak at approximately 181 ppm hasvirtually disappeared. The material is dissolved in water and adjustedto a pH of approximately 7.5 with methanesulfonic acid to form about a23% stock solution.

A typical mass spectrometry analysis of the resulting solution is givenbelow. As can be seen, the resulting material is a mixture oflysine/hexamethylenediamine condensates having various molecular weightsand molar ratios. Moreover, the mixture can comprise from about 0.1% toabout 85% by weight of high molecular weight polymers, in this casepolylysine having a molecular weight of greater than about 1,000. TableI below lists only the lower molecular weight oligomers. The “% ofmixture” is the percent by weight of the specified molecule based on thetotal weight of the low molecular weight oligomers, i.e., the highermolecular weight polylysine has been excluded from the weightcalculations.

TABLE I MW Assignment % of mixture 117 HMDA starting material 2 129lysine starting material that lost water 32 245 X + Y = 1 22 373 X + Y =2 28 501 X + Y = 3 12 629 X + Y = 4 4

Example II

Condensation of L-lysine and epsilon-caprolactam in a molar ratio of 1:1684 g of a 50% aqueous solution of L-lysine (365.2 g, 2.5 mol),epsilon-caprolactam (282.9 g, 2.5 mol), and 1 g sodium hypophosphite areplaced in a 2 l reaction vessel equipped with an efficient stirrer anddistillation head. The solution is heated under a constant stream ofnitrogen to 160° C. for 8 h as water distills from the reaction.Following this, a water pump vacuum is applied for 1 h to removeresidual amounts of solvent and volatile products. The reddish, slightlyviscous melt is cooled to 125° C. and 400 g water are added slowly toresult in a clear orange solution. This solution is further cooled toroom temperature to give a low viscous liquid. 500 g of this solution isadjusted to a pH of approximately 7.5 with concentrated sulfuric acid846 g to form an 53.7% stock solution. The molecular weight of thispolymer is determined to be M_(w)=3990.

Example III

Condensation of L-lysine and aminocaproic acid in a molar ratio of 1:1719 g of a 60% aqueous solution of L-lysine (382.7 g, 2.62 mol),aminocaproic acid (344.8 g, 2.62 mol), and 1 g sodium hypophosphite areplaced in a 2 l reaction vessel equipped with an efficient stirrer anddistillation head. The solution is heated under a constant stream ofnitrogen to 170° C. for 6 h as water distills from the reaction.Following this, a water pump vacuum is applied for 1 h to removeresidual amounts of solvent and volatile products. The reddish, slightlyviscous melt is cooled to 140° C. and 250 g water is added slowly toresult in a clear orange solution. This solution is further cooled toroom temperature to give al low viscous liquid. 500 g of this solutionis adjusted to a pH of approximately 7.5 with concentrated sulfuric acid(46 g) to form about 65.7% stock solution. The molecular weight of thispolymer is determined to be M_(w)=2480.

Example IV

Condensation of L-lysine and aminocaproic acid in a molar ratio of 1:1L-lysine monohydrate (656.8 g, 4.0 mol), aminocaproic acid (524.7 g, 4.0mol) and sodium hypophosphite (0.1 g) are placed in a pressurizable 2.5l reaction vessel and blanketed with nitrogen. The reaction vessel isthen sealed pressure tight and heated to 200° C. for 7 h, during whichtime the internal pressure rises to 7.65 bar. The pressure is thenslowly released to atmospheric pressure to remove water from thereaction mixture. The reaction is then continued for 30 min at 180° C.and atmospheric pressure. The material solidifies upon cooling toambient temperature. An aliquot of this material is dissolved in waterand adjusted to a pH of approximately 7.5 with concentrated sulfuricacid to form an approx. 54% stock solution. The molecular weight of thepolymer is determined to be M_(w)=3550.

Example V

Condensation of L-lysine and aminocaproic acid in molar ratio of 1:1124.8 g of a 60% aqueous solution of L-lysine monohydrate (74.9 g, 0.46mol), aminocaproic acid (59.8 g, 0.46 mol) and sodium hypophosphite (0.1g) are placed in a pressurizable 0.5 l reaction vessel and blanketedwith nitrogen. The reaction vessel is then sealed pressure tight andheated to 167° C. for 4 h, during which time the internal pressure risesto 3.1 bar. The pressure is then slowly released to atmospheric pressureto remove water from the reaction mixture. The reaction is thencontinued for 3 h at 170° C. at atmospheric pressure. The orange,slightly viscous melt is cooled to room temperature and 100 ml water isadded to form a yellow solution. This solution is adjusted to a pH ofapproximately 7.5 with concentrated sulfuric acid (15 mL) to form andapprox. 54% stock solution. The molecular weight of the polymer isdetermined to be M_(w)=740.

Example VI

Condensation of L-lysine and octylamine in a molar ratio of 3:1 L-lysinemonohydrate (656.8 g, 4.0 mol), octylamine (524.7 g, 1.33 mol) andsodium hypophosphite (0.1 g) are placed in a pressurizable 2.5 lreaction vessel and blanketed with nitrogen. The reaction vessel is thensealed pressure tight and heated to 200° C. for 7 h, during which timethe internal pressure rises to 10.90 bar. The pressure is then slowlyreleased to atmospheric pressure to remove volatile materials from thereaction mixture. The reaction is then continued for 30 min at 180° C.and atmospheric pressure. Water (700 mL) is added to the reactionmixture upon cooling to room temperature. An aliquot of this solution isadjusted to a pH of approximately 7.5 with concentrated sulfuric acid toform an approx. 50% stock solution. The molecular weight of the polymeris determined to be M_(w)=850.

Example VII

Base liquid and granular detergent compositions were prepared. Variousamino acid based polymer, oligomer or copolymer materials were added tothe base detergent compositions as described below.

Liquid Detergent Test Composition Preparation

Several heavy duty liquid detergent compositions are prepared containingvarious amino acid based polymer, oligomer or copolymer materials asdescribed in claim 1. Such liquid detergent compositions all have thefollowing basic formula:

TABLE VII Component Wt. % C₁₂₋₁₅ alkyl ether (2.5) sulfate 19 C₁₂₋₁₃alkyl ethoxylate (9.0) 2 C₁₂₋₁₄ glucose amide 3.5 Citric Acid 3 C₁₂₋₁₄Fatty Acid 2 MEA to pH 8 Ethanol 3.4 Propanediol 6.5 Borax 2.5Dispersant 1.2 Na Toluene Sulfonate 2.5 Amino Acid Based FabricTreatment Materials as shown in See Table XI Table XI Dye, Perfume,Brighteners, Enzymes, Preservatives, Suds Balance Suppressor, OtherMinors, Water 100%

Example X

Granular Detergent Test Composition Preparation

Several granular detergent compositions are prepared containing variousamino acid based polymer, oligomer or copolymer materials. Such granulardetergent compositions all have the following basic formula:

Component Wt. % C₁₂ Linear alkyl benzene sulfonate 9 C₁₄₋₁₅ alkylsulfonate 13 Zeolite Builder 28 Sodium Carbonate 27 PEG 4000 1.6Dispersant 2.3 C₁₂₋₁₃ alkyl ethoxylate (E9) 1.5 Sodium Perborate 1.0Soil Release Polymer 0.4 Enzymes 0.6 Amino Acid Based Fabric TreatmentMaterials as shown in See Table XI Table XI Perfume, Brightener, SudsSuppressor, Other Minors, Balance Moisture, Sulfate 100%

Example XI

TABLE XI Example Compositions Polymer Detergent Polymer level FormLysine/HMDA* 5:1  0.5% liquid condensate Lysine/HMDA 5:1 condensate0.75% liquid Lysine/HMDA 5:1 condensate 1.00% liquid Lysine/HMDA 5:1condensate 2.00% liquid Lysine/HMDA 10:1 2.00% liquid condensateLysine/HMDA 3:1 condensate 2.00% liquid Polylysine 2.00% liquidLysine/HMDA 5:1 condensate 2.00% powder Lysine/HMDA 5:1 condensate 4.00%powder Lysine/HMDA 3:1 condensate 2.00% powder Lysine/HMDA 1:1 0.75%liquid Lysine/octylamine 1:1 0.75% liquid Lysine/octylamine 2:1 0.75%liquid Lysine/octylamine 11:1 0.75% liquid Lysine/monoethanolamine 1:10.75% liquid Lysine/monoethanolamine 0.75% liquid 1.7:1Lysine/monoethanolamine 0.75% liquid 7.7:1 Lysine/tryptamine 5:1 0.75%liquid Lysine/tryptophan 5:1 0.75% liquid Lysine/octamethylenediamine0.75% liquid 5:1 Lysine/diaminododecane 5:1 0.75% liquid *HMDA =hexamethylenediamine

What is claimed is:
 1. A detergent composition comprising: a) from 1% to80% by weight, of a detersive surfactant selected from the groupconsisting of nonionic, anionic, cationic, amphoteric, zwitterionicsurfactants, and mixtures thereof; and b) from 0.1% to 10% by weight, ofan admixture of two or more oligomers, polymers or copolymers which areformed from the self-condensation of lysine or the reaction of lysinewith one or more amino acids or amino acid pre-cursors selected from thegroup consisting of ornithine, histidine, tryptophan, a C₂-C₁₂ α,ω-aminoacid, valerolactam, caprolactam, and mixtures thereof; or the reactionof lysine with one or more C₂-C₁₂ α,ω-diamines.
 2. A compositionaccording to claim 1 wherein said oligomer is a admixture formed fromthe reaction of from 1 to 5 equivalents of lysine with from 1 to 5equivalents of a C₂-C₁₂ α,ω-amino acid, valerolactam, caprolactam, andmixtures thereof.
 3. A composition according to claim 2 wherein saidoligomer is formed from the reaction of from 1 to 5 equivalents oflysine with from 1 to 5 equivalents of 1,6-hexamethylenediamine.
 4. Acomposition according to claim 2 wherein said oligomer is formed fromthe reaction of from 1 to 5 equivalents of lysine with from 1 to 5equivalents of caprolactam.
 5. A composition according to claim 1comprising from 0.2% to 8% of said polymer, oligomer, or copolymeradmixture.
 6. A composition according to claim 5 comprising from 0.3% to6% of said polymer, oligomer, or copolymer admixture.
 7. A compositionaccording to claim 6 comprising from 0.4% to 5% of said polymer,oligomer, or copolymer admixture.
 8. A composition according to claim 1wherein said said polymer, oligomer, or copolymer admixture comprisiesat least 5 mole % of a basic amino acid selected from the groupconsisting lysine, ornithine, tryptophan, histidine, and mixturesthereof.
 9. A composition according to claim 8 wherein said saidpolymer, oligomer, or copolymer admixture comprisies at least 10 mole %of a basic amino acid selected from the group consisting lysine,ornithine, tryptophan, histidine, and mixtures thereof.
 10. Acomposition according to claim 9 wherein said said polymer, oligomer, orcopolymer admixture comprisies at least 20 mole % of a basic amino acidselected from the group consisting lysine, ornithine, tryptophan,histidine, and mixtures thereof.
 11. A composition according to claim 10wherein said said polymer, oligomer, or copolymer admixture comprisiesat least 40 mole % of a basic amino acid selected from the groupconsisting lysine, ornithine, tryptophan, histidine, and mixturesthereof.
 12. A detergent composition comprising: a) from 1% to 80% byweight, of a detersive surfactant selected from the group consisting ofnonionic, anionic, cationic, amphoteric, zwitterionic surfactants, andmixtures thereof; and b) from 0.1% to 10% by weight, of an admixture oftwo or more oligomers, polymers or copolymers which are formed from thepolymerization of lysine and one or more polymerizable compoundsselected from the group consisting of hexamethylene diamine, octylamine,nomoethanolamine, tryptamine, tryptophan, octamethylene diamine,diaminododecane, decylamine, docecylamine, and mixtures thereof.
 13. Acomposition according to claim 12 wherein the ratio of lysine to saidpolymerizable compound is 10:1.
 14. A composition according to claim 13wherein the ratio of lysine to said polymerizable compound is 5:1.
 15. Acomposition according to claim 14 wherein the ratio of lysine to saidpolymerizable compound is 2:1.